CN110036092A - 预处理和转化烃的方法 - Google Patents

预处理和转化烃的方法 Download PDF

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CN110036092A
CN110036092A CN201780075338.5A CN201780075338A CN110036092A CN 110036092 A CN110036092 A CN 110036092A CN 201780075338 A CN201780075338 A CN 201780075338A CN 110036092 A CN110036092 A CN 110036092A
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charging
fouling
hydrocarbon
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W·德尔克斯
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Shell Internationale Research Maatschappij BV
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Abstract

本发明提供一种预处理烃蒸汽裂化器进料的方法，所述方法包含使所述进料与溶剂接触以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器的预热、对流和辐射部分中结垢和具有增加含量的结垢组分的富溶剂。本发明进一步提供一种蒸汽裂化烃的方法，所述方法包含：a)向工艺中进料烃蒸汽裂化器进料；b)通过使所述进料与溶剂接触来预处理所述进料以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器中结垢和具有增加含量的结垢组分的富溶剂；c)加热所述预处理的进料；和d)使所述预处理的进料通过在裂化条件下的蒸汽裂化器以产生裂化产物。

Description

预处理和转化烃的方法
技术领域
本发明涉及一种预处理烃蒸汽裂化器进料的方法和蒸汽裂化烃的方法。
背景技术
通常，乙烯和丙烯是通过链烷烃原料的蒸汽裂化制备，所述链烷烃原料包括乙烷、丙烷、石脑油和蜡油。
欧洲专利申请公开案0 697 455描述用于快速冷却来自蒸汽裂化器的流出物的输送管线交换器的结垢。这是决定裂化器运行长度的主要因素。结垢可能是由进料中，特别是在例如蜡油的进料中，以及在裂化炉中热解期间形成的焦油中芳香族化合物的含量引起的。
US 2008/0194900教示一种通过将所述物流进料到加氢处理器以去除杂质并且然后将所述物流传递到芳香族物萃取单元以产生脱芳香族物石脑油物流来改质石脑油物流的方法。然后将这种脱芳香烃石脑油物流进料到裂化过程中。
发明内容
本发明提供一种预处理烃蒸汽裂化器进料的方法，所述方法包含使所述进料与溶剂接触以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器的预热、对流和辐射部分中结垢和具有增加含量的结垢组分的富溶剂。
本发明进一步提供一种蒸汽裂化烃的方法，所述方法包含：a)向所述过程中进料烃蒸汽裂化器进料；b)通过使所述进料与溶剂接触来预处理所述进料以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器中结垢和具有增加含量的结垢组分的富溶剂；c)加热所述预处理的进料；和d)使所述预处理的进料通过在裂化条件下的蒸汽裂化器以产生裂化产物。
附图说明
图1描绘在实验室规模的输送管线交换器中形成的焦炭层。
具体实施方式
本发明提供一种具有较高氢气含量的蒸汽裂化器进料，其产生得到改善的来自蒸汽裂化器的产物构成。下游设备，特别是输送管线交换器(TLE)中的结垢量减少，这导致更长的运行时间而没有维护停机，并且改善了交换器中的热传递。据信额外优点会是来自萃取的剩余液体可用于降低骤冷油部分中的粘度。
本发明提供一种预处理烃蒸汽裂化器进料的方法。烃物流裂化器进料包含一种或多种烃，优选为链烷烃。原料可包含非链烷烃，例如烯烃，按烃的总重量计，其量优选小于10重量％。进料可另外包含来自所述过程的再循环物流。
在一个实施例中，烃蒸汽裂化器进料可包含蜡油、加氢处理的真空瓦斯油、瓦斯油、疏松石蜡或其混合物。蜡油是通过真空闪蒸馏出物流的加氢裂化产生的氢化残余物。松驰蜡是一种从脱蜡单元中获得的链烷烃物流，其用于产生润滑剂和链烷烃。
在另一个实施例中，烃蒸汽裂化器进料可包含来自塑料废物的热解油。这种物流具有大浓度的污染物，使其成为非常低价值的物流。
烃蒸汽裂化器进料还包含结垢组分，其导致蒸汽裂化器的下游部分结垢。这种结垢可能发生在裂化器的预热、对流和/或辐射部分中，或者其可能在下游热交换和/或分离设备中形成。这些结垢组分可包括会在设备中引起焦化或结垢的任何组分。当来自蒸汽裂化器的产物冷却时，这些结垢组分可在输送管线交换器中冷凝。这些结垢组分的实例包括多环芳香族物、树脂和其混合物。
烃蒸汽裂化器进料还可包含污染物，其会导致裂化产物处理部分出现问题。这些污染物可包括氮、钒、氯、氧、硫或其化合物。这些污染物也可以通过与溶剂接触从烃蒸汽裂化器进料中去除。
通过使进料与溶剂接触来预处理烃蒸汽裂化器进料。进料可以在容器中、在管道中或以所属领域普通技术人员已知的用于进行溶剂萃取步骤的另一种方式与溶剂接触。
进行预处理的合适溶剂的实例包括糠醛、环丁砜、甲苯、N-甲酰基吗啉、N-甲基吡咯烷酮、四乙二醇和二甲亚砜。
在一个实施例中，可以从富溶剂中去除结垢组分。这些结垢组分可以在蒸汽裂化器系统的另一部分中用作骤冷油流。结垢组分也可用于降低重沥青和/或裂化瓦斯油流的粘度。
使烃蒸汽裂化器进料与溶剂接触后，预处理的进料具有减少的结垢组分含量。在与溶剂接触之前，预处理的进料具有比烃蒸汽裂化器进料更高的氢气含量。富溶剂具有增加的结垢组分含量。
与溶剂接触后，预处理的进料优选具有75％或更少的烃蒸汽裂化器进料中的结垢组分的量、更优选60％或更少、并且最优选50％或更少的烃蒸汽裂化器进料中的结垢组分。
通常将预处理的进料预热。可以使用热交换器、熔炉或传热和/或加热装置的任何其它组合来加热进料。
预处理的原料在处于裂化条件下的裂化区中蒸汽裂化，以至少产生烯烃和氢气。裂化区可包含所属领域已知的任何裂化系统，其适于裂化预处理的原料。裂化区可包含一个或多个熔炉，每个熔炉专用于进料的特定进料或馏分。
所述裂化步骤在高温下、优选在650℃到1000℃的范围内、更优选在750℃到850℃的范围内进行。通常将蒸汽加入裂化区，充当稀释剂以降低烃分压，从而提高烯烃产率。蒸汽还减少裂化区中含碳材料或焦炭的形成和沉积。在没有氧气的情况下发生裂化。在裂化条件下的停留时间非常短，通常为毫秒级。
从裂化器中获得裂化器流出物，其可包含芳香族物、烯烃、氢气、水、二氧化碳和其它烃化合物。所获得的具体产物视进料的组成、烃与蒸汽比率和裂化温度以及熔炉停留时间而定。然后将来自蒸汽裂化器的裂化产物通过一个或多个热交换器(通常称为TLE)，以快速降低裂化产物的温度。TLE优选将裂化产物冷却到400到550℃的温度。
实例
以下实例在实验室规模的蒸汽裂化器单元中进行。泵将来自温度控制的进料容器的烃进料到蒸发器中。将烃物流与气态惰性物流混合，并且将混合物加热到380与550℃之间的温度。在这一温度下将进料蒸发，并且然后在通常为700到850℃的范围内的温度下将其进料到盘管/反应器中。
将产物流从盘管/反应器中去除并且在输送管线交换器(TLE)中从约600℃的温度冷却到约300-350℃的温度。结垢组分在TLE的壁上冷凝并且可以热分解成焦炭层。
来自TLE的气流在单独的骤冷容器中进一步冷却到约40℃，并且然后可以分析这一物流。
壁上的焦炭层的厚度可以通过测量空管的壁厚和结垢管的壁厚并且减去空管厚度来计算。
实例
通过在上述设备中裂化样品进行三个实例。表1中示出样品裂化前的各种特征，并且针对图1中的每个实例示出在裂化器下游的TLE中形成的焦炭层。
在实例1中，蜡油裂化。
在实例2中，首先使与实例1中相同的蜡油与糠醛接触，以萃取至少一部分结垢组分，并且然后裂化。
在实例3中，使与实例1的相同的蜡油与糠醛接触以萃取至少一部分结垢组分。将这一萃取步骤再重复两次(总共萃取三次)。然后这种蜡油裂化。
表1
特征(如在70℃下测量) 实例1 实例2 实例3
密度(kg/l) 0.8188 0.815 0.812
折射率 1.4548 1.4514 1.4500
氢气含量(重量％) 13.82 13.92 14.05
硫(重量％) 0.003 0.0023 0.0017

Claims (11)

1.一种预处理烃蒸汽裂化器进料的方法，所述方法包含使所述进料与溶剂接触以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器的预热、对流和辐射部分中结垢和具有增加含量的结垢组分的富溶剂。
2.根据权利要求1所述的方法，其中所述烃蒸汽裂化器进料包含蜡油、加氢处理的真空瓦斯油、瓦斯油、疏松石蜡或其混合物。
3.根据权利要求1所述的方法，其中所述烃蒸汽裂化器进料包含来自塑料废物的热解油。
4.根据权利要求1至2中任一项所述的方法，其中所述结垢组分包含多环芳香族物、树脂或其混合物。
5.根据权利要求1至3中任一项所述的方法，其中所述预处理的进料具有比所述烃蒸汽裂化器进料更高的氢气含量。
6.根据权利要求1至4中任一项所述的方法，其中所述结垢组分通过在输送管线交换器中冷凝而导致结垢。
7.根据权利要求1至5中任一项所述的方法，其中所述溶剂选自由以下组成的群组：糠醛、环丁砜、甲苯、N-甲酰基吗啉、N-甲基吡咯烷酮、四乙二醇和二甲亚砜。
8.根据权利要求1至6中任一项所述的方法，其进一步包含从所述富溶剂中去除所述结垢组分，并且在所述蒸汽裂化系统的另一部分中使用那些组分作为骤冷油流或用于降低重沥青和/或裂化瓦斯油流的粘度。
9.一种蒸汽裂化烃的方法，其包含：
a.向工艺中进料烃蒸汽裂化器进料；
b.通过使所述进料与溶剂接触来预处理所述进料以产生具有减少含量的结垢组分的预处理的进料，所述结垢组分导致在所述蒸汽裂化器的预热、对流和辐射部分中结垢和具有增加含量的结垢组分的富溶剂；
c.加热所述预处理的进料；和
d.使所述预处理的进料通过在裂化条件下的蒸汽裂化器以产生裂化产物。
10.根据权利要求8所述的方法，其进一步包含使所述裂化产物通过一个或多个热交换器以降低所述裂化产物的温度。
11.根据权利要求8至9中任一项所述的方法，其中所述裂化条件包含700到900℃的范围内的温度。
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